EP0601438B1 - Process for the preparation of polyacylated aromatics - Google Patents

Process for the preparation of polyacylated aromatics Download PDF

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EP0601438B1
EP0601438B1 EP93119254A EP93119254A EP0601438B1 EP 0601438 B1 EP0601438 B1 EP 0601438B1 EP 93119254 A EP93119254 A EP 93119254A EP 93119254 A EP93119254 A EP 93119254A EP 0601438 B1 EP0601438 B1 EP 0601438B1
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compounds
alkyl
iii
aromatics
formula
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EP0601438A1 (en
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Wolfgang Dr. Siegel
Jochen Dr. Schroeder
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group

Definitions

  • a direct double Friedel-Crafts acylation of trimethyl- and tetramethylbenzenes in the presence of AlCl 3 is from Org. Prep. Proc. Int. 10 (1978) 255 and disclosed in GB-A 22 35 195 for 1,2,4,5-tetramethylbenzene derivatives.
  • Zh describes the direct reaction of anisole, a strongly activated aromatic, with benzoyl chloride in the presence of iron powder to give 2,4-dibenzoylanisole.
  • anisole a strongly activated aromatic
  • benzoyl chloride in the presence of iron powder to give 2,4-dibenzoylanisole.
  • the object was to provide a process which makes it possible to introduce further acyl groups into unsubstituted or C 1 -C 4 -alkyl-substituted acyl aromatics without the need for equimolar amounts of Friedel-Crafts catalysts.
  • Another object was to find a process which allows the direct preparation of multiply acylated aromatics with only catalytic amounts of aromatics catalysts in only one process step.
  • the starting compounds II are known per se or can be obtained by known methods. These are corresponding phenyl or C 1 -C 4 alkyl-substituted phenyl compounds.
  • the Substituents R 2 are e.g. As ethyl, n-propyl and n-butyl, but preferably methyl.
  • the compound II is prepared in situ from aromatics IV:
  • aromatics are compounds such as benzene, toluene, o-xylene, m-xylene, p-xylene and especially tri- and tetra-C 1 -C 4 -alkyl-substituted benzenes such as 1,3,5-trimethylbenzene (mesitylene ), 1,3,5-triethylbenzene, 1,2,4,5-tetramethylbenzene (durol) and 1,2,3,5-tetramethylbenzene (isodurol).
  • 1,3,5-trimethylbenzene mesitylene
  • 1,3,5-triethylbenzene 1,2,4,5-tetramethylbenzene
  • durol 1,2,3,5-tetramethylbenzene
  • isodurol 1,2,3,5-tetramethylbenzene
  • carboxylic acid halides III of which the chlorides are preferred.
  • carboxylic acid halides III of which the chlorides are preferred.
  • benzoyl halides or those benzoyl halides which have substituents which are inert on the phenyl radical under the reaction conditions such as nitro, halogen such as fluorine, chlorine and bromine, C 1 -C 6 alkoxy groups such as methoxy and C 1 -C 4 alkyl groups such as methyl carry.
  • aliphatic C 1 -C 6 - ⁇ -halocarboxylic acids such as 2-halo-acetic and 2-halo-propionic acid can be used in the process according to the invention.
  • benzoyl chloride 4-fluorobenzoyl chloride, 4-chlorobenzoyl chloride, 4-nitrobenzoyl chloride, 2-methylbenzoyl chloride and chloroacetyl chloride.
  • Fe (II) compounds such as FeSO 4 , Fe (III) compounds such as Fe 2 O 3 , FeCl 3 , FeBr 3 , Fe 2 (SO 4 ) 3 , iron carboxylates such as iron (III) acetate, iron ( III) acetylacetonate, of course also mixed-valent iron compounds such as Fe 3 O 4 , furthermore zinc (II) compounds such as ZnO, ZnCl 2 , ZnBr 2 , ZnSO 4 , zinc carboxylates such as zinc benzoate and zinc acetate, molybdenum and tungsten (VI) - Compounds such as MoO 3 and WO 3 and tin (IV) compounds such as tin tetrachloride or bromide.
  • the iron compounds are preferred as catalysts, especially iron oxide Fe 2 O 3 .
  • the compounds mentioned can be used in free form, but also bound to inert carriers. Examples of suitable carriers are silicon
  • the molar ratios of compounds II and III can vary according to the desired degree of acylation. For acylation of aromatics II already carrying acyl groups, however, the ratios are generally from 1: 1 to 1.3: 1 equivalents Carboxylic acid halide for aromatics. An excess is generally used for double acylations, so that the molar amounts here are between 3: 1 and 10: 1 for III: II. If one starts directly from aromatics IV, at least one equivalent more carboxylic acid halide must be used accordingly.
  • the catalyst can be used in amounts of 0.01 to 20 mol%, preferably 0.1 to 3 mol%, based on the amount of the acylaromatic II or the aromatic IV.
  • the reaction temperature is generally 40 to 250 ° C, preferably 80 to 200 ° C and particularly preferably 100 to 180 ° C.
  • the reaction can therefore be carried out at 1 to 10 bar, but normal pressure is preferred.
  • the reaction can be carried out by heating to the reaction temperature. However, it is preferred to submit the starting material II or IV and the catalyst and to add the carboxylic acid halide III at elevated temperature.
  • reaction can take place without a solvent, but inert solvents such as nitrobenzene or hydrocarbons can also be used.
  • the reaction is generally complete after 2 to 6 hours.
  • the products are isolated by known methods such as distillation or crystallization.
  • the process according to the invention allows the production of multiply acylated aromatics from an acyl aromatic and carboxylic acid halides in good yields. Only catalytic amounts of a metal compound are needed for this. The reaction can be carried out without a solvent and requires no hydrolytic work-up. Furthermore, the invention allows the production of multiply acylated aromatics from benzene or C 1 -C 4 alkyl-substituted benzenes.
  • the products produced according to the process are used as monomer units for polyaryl ethers (GB 2 235 195).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Description

Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von mehrfach acylierten Aromaten der allgemeinen Formel I

Figure imgb0001
in der die Variablen folgende Bedeutung haben:

R1
Phenyl oder inerte Substituenten tragendes Phenyl, α-Halogen-C1-C6-Alkyl, wobei diese Reste gleich oder verschieden sein können;
R2
C1-C4-Alkyl,
m
2 oder 3;
n
0 bis 4, wobei die Substituenten R2 verschieden sein können, wenn n > 1 ist,
mit der Maßgabe, daß m + n ≼ 6
Figure imgb0002
 ist.The present invention relates to a new process for the preparation of multi-acylated aromatics of the general formula I.
Figure imgb0001
 in which the variables have the following meaning:
R 1
Phenyl or phenyl which carries inert substituents, α-halo-C 1 -C 6 -alkyl, these radicals being able to be identical or different;
R 2
C 1 -C 4 alkyl,
m
2 or 3;
n
0 to 4, where the substituents R 2 can be different if n> 1,
with the proviso that m + n ≼ 6
Figure imgb0002
 is.

Die Einführung einer zweiten Acylgruppe in Acylaromaten ist dadurch erschwert, daß Acylgruppen den Aromaten für weitere Friedel-Crafts-Acylierungen desaktivieren.The introduction of a second acyl group in acylaromatics is complicated by the fact that acyl groups deactivate the aromatic for further Friedel-Crafts acylations.

In Zh. Org. Khim. 6 (1970) 532 wird beschrieben, daß eine weitere Benzoylgruppe durch Reaktion mit Benzoylchlorid in Gegenwart katalytischer Mengen feinverteilten Eisenpulvers oder FeCl3 in hochaktiviertes 2,4-Dimethoxybenzophenon eingeführt werden kann.In Zh. Org. Khim. 6 (1970) 532 describes that a further benzoyl group can be introduced into highly activated 2,4-dimethoxybenzophenone by reaction with benzoyl chloride in the presence of catalytic amounts of finely divided iron powder or FeCl 3 .

Eine direkte zweifache Friedel-Crafts-Acylierung von Trimethyl- und Tetramethylbenzolen in Gegenwart von AlCl3 ist aus Org. Prep. Proc. Int. 10 (1978) 255 bekannt und für 1,2,4,5-Tetramethylbenzolderivate in der GB-A 22 35 195 offenbart. Dazu werden große molare Überschüsse an Carbonsäurechlorid und AlCl3 benötigt, die nicht nur unwirtschaftlich sind, sondern auch bei der üblichen hydrolytischen Aufarbeitung zu salzsäurehaltigen Abwässern führen, die eine aufwendige Entsorgung nach sich ziehen.A direct double Friedel-Crafts acylation of trimethyl- and tetramethylbenzenes in the presence of AlCl 3 is from Org. Prep. Proc. Int. 10 (1978) 255 and disclosed in GB-A 22 35 195 for 1,2,4,5-tetramethylbenzene derivatives. This requires large molar excesses of carboxylic acid chloride and AlCl 3 , which are not only uneconomical, but also lead to hydrochloric acid-containing wastewater in the usual hydrolytic workup, which entails complicated disposal.

Die direkte Umsetzung von Anisol, einem stark aktivierten Aromaten, mit Benzoylchlorid in Gegenwart von Eisenpulver zu 2,4-Dibenzoylanisol beschreibt Zh. Org. Khim. 6 (1970) 535.Zh describes the direct reaction of anisole, a strongly activated aromatic, with benzoyl chloride in the presence of iron powder to give 2,4-dibenzoylanisole. Org. Khim. 6 (1970) 535.

Die einfache Acylierung von Aromaten mit katalytischen Mengen FeCl3, Jod, ZnCl2 und Eisenpulver ist aus Synthesis (1972) 533 bekannt.The simple acylation of aromatics with catalytic amounts of FeCl 3 , iodine, ZnCl 2 and iron powder is known from Synthesis (1972) 533.

Es bestand die Aufgabe, ein Verfahren zur Verfügung zu stellen, das es erlaubt, weitere Acylgruppen in unsubstituierte oder C1-C4-alkylsubstituierte Acylaromaten einzuführen, ohne daß dazu äquimolare Mengen an Friedel-Crafts-Katalysatoren benötigt werden. Weiterhin bestand die Aufgabe, ein Verfahren zu finden, das die unmittelbare Herstellung von mehrfach acylierten Aromaten mit nur katalytischen Mengen an Katalysatoren aus Aromaten in nur einem Verfahrensschritt erlaubt.The object was to provide a process which makes it possible to introduce further acyl groups into unsubstituted or C 1 -C 4 -alkyl-substituted acyl aromatics without the need for equimolar amounts of Friedel-Crafts catalysts. Another object was to find a process which allows the direct preparation of multiply acylated aromatics with only catalytic amounts of aromatics catalysts in only one process step.

Diese Aufgabe wurde durch das oben definierte Verfahren gelöst, das dadurch gekennzeichnet ist, daß man Acylaromaten der allgemeinen Formel II

Figure imgb0003
in der p für 1 oder 2 steht, mit einer dem gewünschten Acylierungsgrad entsprechenden Menge an einem Carbonsäurehalogenid der allgemeinen Formel III
Figure imgb0004
 in der X für Halogen steht, in Gegenwart von Fe(II),-Fe(III)-, Zn(II)-, Mo(VI)-, W(VI)- oder Sn(IV)-Verbindungen umsetzt.This object was achieved by the process defined above, which is characterized in that acyl aromatics of the general formula II
Figure imgb0003
 in which p represents 1 or 2, with an amount of a carboxylic acid halide of the general formula III corresponding to the desired degree of acylation
Figure imgb0004
 in which X represents halogen, in the presence of Fe (II), Fe (III), Zn (II), Mo (VI), W (VI) or Sn (IV) compounds.

Schematisch läßt sich das Verfahren durch folgende Reaktionsgleichung wiedergeben:

Figure imgb0005
The process can be represented schematically by the following reaction equation:
Figure imgb0005

Die Ausgangsverbindungen II sind an sich bekannt oder nach bekannten Methoden erhältlich. Es handelt sich um entsprechende Phenyl- oder C1-C4-alkylsubstituierte Phenylverbindungen. Die Substituenten R2 sind z. B. Ethyl, n-Propyl und n-Butyl, vorzugsweise aber Methyl.The starting compounds II are known per se or can be obtained by known methods. These are corresponding phenyl or C 1 -C 4 alkyl-substituted phenyl compounds. The Substituents R 2 are e.g. As ethyl, n-propyl and n-butyl, but preferably methyl.

In einer besonders bevorzugten Ausführungsform wird die Verbindung II in situ aus Aromaten IV hergestellt:

Figure imgb0006
In a particularly preferred embodiment, the compound II is prepared in situ from aromatics IV:
Figure imgb0006

Bei diesen Aromaten handelt es sich um Verbindungen wie Benzol, Toluol, o-Xylol, m-Xylol, p-Xylol und vor allem tri- und tetra-C1-C4-alkylsubstituierte Benzole wie 1,3,5-Trimethylbenzol (Mesitylen), 1,3,5-Triethylbenzol, 1,2,4,5-Tetramethylbenzol (Durol) und 1,2,3,5-Tetramethylbenzol (Isodurol).These aromatics are compounds such as benzene, toluene, o-xylene, m-xylene, p-xylene and especially tri- and tetra-C 1 -C 4 -alkyl-substituted benzenes such as 1,3,5-trimethylbenzene (mesitylene ), 1,3,5-triethylbenzene, 1,2,4,5-tetramethylbenzene (durol) and 1,2,3,5-tetramethylbenzene (isodurol).

Die Verbindungen II bzw. IV werden mit Carbonsäurehalogeniden III umgesetzt, von denen die Chloride bevorzugt sind. Es kommen zum einen Benzoylhalogenide oder solche Benzoylhalogenide in Betracht, die am Phenylrest unter den Reaktionsbedingungen inerte Substituenten wie Nitro-, Halogen wie Fluor, Chlor und Brom, C1-C6-Alkoxygruppen wie Methoxy und C1-C4-Alkylgruppen wie Methyl tragen. Weiterhin können aliphatische C1-C6-α-Halogencarbonsäuren wie 2-Halogen-Essig- und 2-Halogen-Propionsäure im erfindungsgemäßen Verfahren eingesetzt werden. Als bevorzugte Beispiele seien genannt: Benzoylchlorid, 4-Fluorbenzoylchlorid, 4-Chlorbenzoylchlorid, 4-Nitrobenzoylchlorid, 2-Methylbenzoylchlorid und Chloracetylchlorid.The compounds II and IV are reacted with carboxylic acid halides III, of which the chlorides are preferred. On the one hand there are benzoyl halides or those benzoyl halides which have substituents which are inert on the phenyl radical under the reaction conditions, such as nitro, halogen such as fluorine, chlorine and bromine, C 1 -C 6 alkoxy groups such as methoxy and C 1 -C 4 alkyl groups such as methyl carry. Furthermore, aliphatic C 1 -C 6 -α-halocarboxylic acids such as 2-halo-acetic and 2-halo-propionic acid can be used in the process according to the invention. The following may be mentioned as preferred examples: benzoyl chloride, 4-fluorobenzoyl chloride, 4-chlorobenzoyl chloride, 4-nitrobenzoyl chloride, 2-methylbenzoyl chloride and chloroacetyl chloride.

Die Reaktion wird durch eine Reihe definitionsgemäßer Metallverbindungen katalysiert. In Betracht kommen Fe(II)-Verbindungen wie FeSO4, Fe(III)-Verbindungen wie Fe2O3, FeCl3, FeBr3, Fe2(SO4)3, Eisencarboxylate wie Eisen(III)-Acetat, Eisen (III)-acetylacetonat, natürlich auch gemischt-valente Eisenverbindungen wie Fe3O4, weiterhin Zink(II)-Verbindungen wie ZnO, ZnCl2, ZnBr2, ZnSO4, Zinkcarboxylate wie Zinkbenzoat und Zinkacetat, Molybdän- und Wolfram(VI)-Verbindungen wie MoO3 und WO3 sowie Zinn(IV)-Verbindungen wie Zinntetrachlorid oder -bromid. Die Eisenverbindungen sind als Katalysatoren bevorzugt, davon besonders Eisenoxid Fe2O3. Die genannten Verbindungen können in freier Form, aber auch an inerte Träger gebunden eingesetzt werden. Als Träger kommen z.B. Siliciumoxid, Aluminiumoxid oder Alumosilikate in Betracht.The reaction is catalyzed by a number of metal compounds as defined. Fe (II) compounds such as FeSO 4 , Fe (III) compounds such as Fe 2 O 3 , FeCl 3 , FeBr 3 , Fe 2 (SO 4 ) 3 , iron carboxylates such as iron (III) acetate, iron ( III) acetylacetonate, of course also mixed-valent iron compounds such as Fe 3 O 4 , furthermore zinc (II) compounds such as ZnO, ZnCl 2 , ZnBr 2 , ZnSO 4 , zinc carboxylates such as zinc benzoate and zinc acetate, molybdenum and tungsten (VI) - Compounds such as MoO 3 and WO 3 and tin (IV) compounds such as tin tetrachloride or bromide. The iron compounds are preferred as catalysts, especially iron oxide Fe 2 O 3 . The compounds mentioned can be used in free form, but also bound to inert carriers. Examples of suitable carriers are silicon oxide, aluminum oxide or aluminosilicates.

Die molaren Verhältnisse der Verbindungen II und III können entsprechend dem gewünschten Acylierungsgrad variieren. Für eine Acylierung von bereits Acylgruppen tragenden Aromaten II liegen die Verhältnisse aber in der Regel bei 1:1 bis 1,3:1 Äquivalenten Carbonsäurehalogenid zum Aromaten. Für Zweifachacylierungen wird im allgemeinen ein Überschuß eingesetzt, so daß die molaren Mengen hier zwischen 3:1 und 10:1 für III:II liegen. Geht man direkt von Aromaten IV aus, muß entsprechend mindestens ein Äquivalent Carbonsäurehalogenid mehr eingesetzt werden.The molar ratios of compounds II and III can vary according to the desired degree of acylation. For acylation of aromatics II already carrying acyl groups, however, the ratios are generally from 1: 1 to 1.3: 1 equivalents Carboxylic acid halide for aromatics. An excess is generally used for double acylations, so that the molar amounts here are between 3: 1 and 10: 1 for III: II. If one starts directly from aromatics IV, at least one equivalent more carboxylic acid halide must be used accordingly.

Der Katalysator kann in Mengen von 0,01 bis 20 mol.-%, vorzugsweise 0,1 bis 3 mol-% bezogen auf die Menge des Acylaromaten II bzw. des Aromaten IV eingesetzt werden.The catalyst can be used in amounts of 0.01 to 20 mol%, preferably 0.1 to 3 mol%, based on the amount of the acylaromatic II or the aromatic IV.

Die Reaktionstemperatur liegt in der Regel bei 40 bis 250°C, bevorzugt bei 80 bis 200°C und besonders bevorzugt bei 100 bis 180°C.The reaction temperature is generally 40 to 250 ° C, preferably 80 to 200 ° C and particularly preferably 100 to 180 ° C.

Der Druck spielt im erfindungsgemäßen Verfahren keine erkennbare Rolle. Die Reaktion kann deshalb bei 1 bis 10 bar ausgeführt werden, bevorzugt ist aber Normaldruck. Die Reaktion kann nach Vermischen der Ausgangsverbindungen und des Katalysators durch Erwärmen auf Reaktionstemperatur erfolgen. Bevorzugt wird aber, den Ausgangsstoff II bzw. IV und den Katalysator vorzulegen und bei erhöhter Temperatur mit dem Carbonsäurehalogenid III zu versetzen.Pressure plays no discernible role in the method according to the invention. The reaction can therefore be carried out at 1 to 10 bar, but normal pressure is preferred. After mixing the starting compounds and the catalyst, the reaction can be carried out by heating to the reaction temperature. However, it is preferred to submit the starting material II or IV and the catalyst and to add the carboxylic acid halide III at elevated temperature.

Die Reaktion kann in einer bevorzugten Ausführungsform ohne Lösungsmittel erfolgen, es können aber auch inerte Lösungsmittel wie Nitrobenzol oder Kohlenwasserstoffe mitverwendet werden.In a preferred embodiment, the reaction can take place without a solvent, but inert solvents such as nitrobenzene or hydrocarbons can also be used.

Die Reaktion ist im allgemeinen nach 2 bis 6 Stunden beendet. Die Isolierung der Produkte erfolgt nach bekannten Methoden wie Destillation oder Kristallisation.The reaction is generally complete after 2 to 6 hours. The products are isolated by known methods such as distillation or crystallization.

Das erfindungsgemäße Verfahren erlaubt die Herstellung mehrfach acylierter Aromaten aus einem Acylaromaten und Carbonsäurehalogeniden in guten Ausbeuten. Dazu werden nur katalytische Mengen einer Metallverbindung gebraucht. Die Reaktion kann ohne Lösungsmittel durchgeführt werden und erfordert keine hydrolytische Aufarbeitung. Weiterhin erlaubt die Erfindung die Herstellung mehrfach acylierte Aromaten aus Benzol oder C1-C4-alkylsubstituierten Benzolen.The process according to the invention allows the production of multiply acylated aromatics from an acyl aromatic and carboxylic acid halides in good yields. Only catalytic amounts of a metal compound are needed for this. The reaction can be carried out without a solvent and requires no hydrolytic work-up. Furthermore, the invention allows the production of multiply acylated aromatics from benzene or C 1 -C 4 alkyl-substituted benzenes.

Die verfahrensgemäß hergestellten Produkte finden als Monomerbausteine für Polyarylether (GB 2 235 195) Verwendung.The products produced according to the process are used as monomer units for polyaryl ethers (GB 2 235 195).

BeispieleExamples Allgemeine Vorschrift für die BeispieleGeneral rule for the examples

1 mol eines substituierten Benzols IV und Katalysator wurden bei der Temperatur T1 mit dem Carbonsäurechlorid III versetzt und für eine Zeit t auf die Temperatur T2 erhitzt. Die Isolierung erfolgte destillativ oder durch Kristallisation aus Heptan.1 mol of a substituted benzene IV and catalyst were mixed with the carboxylic acid chloride III at the temperature T 1 and heated to the temperature T 2 for a time t. The isolation was carried out by distillation or by crystallization from heptane.

Die weiteren Einzelheiten sind der Tabelle zu entnehmen.

Figure imgb0007
Figure imgb0008
Figure imgb0009
 Further details can be found in the table.
Figure imgb0007
Figure imgb0008
Figure imgb0009

Claims (5)

  1. A process for preparing polyacylated aromatic compounds of the formula I
    Figure imgb0018
     where
    R1   is phenyl which is unsubstituted or has inert substituents or is α-halo-C1-C6-alkyl, it being possible for these radicals to be identical or different;
    R2   is C1-C4-alkyl;
    m   is 2 or 3;
    n   is 0 to 4, it being possible for the R2 substituents to be different when n >1,
    with the proviso that m + n ≤ 6
    Figure imgb0019
    , which comprises reacting an acylaromatic compound of the formula II
    Figure imgb0020
     where p is 1 or 2, with a carbonyl halide of the formula III
    Figure imgb0021
     where X is halogen, in an amount appropriate for the desired degree of acylation, in the presence of a catalytic amount of Fe(II), Fe(III), Zn(II), Mo(VI), W(VI) or Sn(IV) compounds.
  2. A process as claimed in claim 1, wherein carbonyl chlorides Cl-CO-R1 are reacted.
  3. A process as claimed in claim 1 or 2, wherein tri- or tetra-C1-C4-alkylacylbenzenes II are reacted.
  4. A process as claimed in claims 1-3, wherein the reaction is carried out in the presence of Fe2O3.
  5. A process for preparing polyacylated aromatic compounds of the formula I
    Figure imgb0022
     where
    R1   is phenyl which is unsubstituted or has inert substituents or is α-halo-C1-C6-alkyl, it being possible for these radicals to be identical or different;
    R2   is C1-C4-alkyl;
    m   is 2 or 3;
    n   is 0 to 4, it being possible for the R2 substituents to be different when n >1,
    with the proviso that m + n ≤ 6
    Figure imgb0023
    , which comprises reacting an aromatic compound of the formula IV
    Figure imgb0024
     with a carbonyl halide of the formula III
    Figure imgb0025
     where X is halogen, in an amount appropriate for the desired degree of acylation, in the presence of a catalytic amount of Fe(II), Fe(III), Zn(II), Mo(VI), W(VI) or Sn(IV) compounds.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE515540C (en) * 1926-12-21 1931-01-28 I G Farbenindustrie Akt Ges Process for the preparation of diacidyl derivatives of meta-xylene
US2322036A (en) * 1939-11-16 1943-06-15 Standard Oil Dev Co Condensation product
US2346926A (en) * 1939-11-16 1944-04-18 Standard Oil Dev Co Condensation product
US2802032A (en) * 1955-06-22 1957-08-06 Monsanto Chemicals 3, 4-dimethylbenzophenone
SU368223A1 (en) * 1970-05-25 1973-01-26 Ю. Юлдашев, Н. Г. Сидорова , Л. И. Леонтьева Ташкентский государственный университет METHOD OF OBTAINING SUBSTITUTED AROMATIC KETONES
SU1016277A1 (en) * 1980-09-12 1983-05-07 Хмельницкий Технологический Институт Бытового Обслуживания Process for preparing mono- or diarylketones
US4922026A (en) * 1988-12-27 1990-05-01 The Dow Chemical Company Acylation process to form diketones
GB8904027D0 (en) * 1989-02-22 1989-04-05 Ici Plc Aromatic compounds

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DE4240966A1 (en) 1994-06-09
US5395975A (en) 1995-03-07
ES2101202T3 (en) 1997-07-01
DE59306180D1 (en) 1997-05-22
JPH06239790A (en) 1994-08-30

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